Metal compound of azo-dyestuffs and process of making same



Patented Nov. 15, 1932 UNITED STATES PATENT OFFICE FRITZ STKAUB, OF BASEL, AND HERMAN N SCHNEIDER AN D HEINRICH BERNHARD, OF

RIEHEN, NEAR BASEIJ, SWITZERLAND, ASSIGNORS T0 SOCIETY OF CHEMICAL IN- DUSTRY. IN'BASLE, 01 BASEL,'SWITZEBLAND' METAL coxrouma or nzomxns'rurrs AND rnocnss or .MAKING SAME,

No Drawing. Application filed September 10, 1928, Se'rialllo. 305,135,an11 in Switzerland September 17,

The present invention relates to the manufacture of metal compounds of azo-dyestufls. It comprises the process of making these compounds themselves, and the material that has been dyed with the new compounds.

By the present invention valuable prodncts-which may be defined as mixed azo dyestuffs containing metals are obtained by causing agents yielding-metal to react on mixtures of such azo-dyestuffs which contain groups capable of fixing metal, or by causing tain ony monoazo-dyestufi's or only polyazodyestu or monoazo-dyestufis together with polyazo-dyestuflt's.

The reaction may occur in neutral, acid or alkaline medium under atmospheric pressure or under increased pressure and in presence or absence of suitable additions, such'as organic or inorganic salts or substances of another kind, such as organic solvents.

As suitable metals there come into consideration those which are at least bivalent and 0 these agents yielding metal may be used single or as mixtures.

The new products may also be made by performing the operation of coupling which produces the dyestufi or dyestuffs in presence of an agent yielding metal.

Finally the new products may be'made inthe dye-bath or on the fibre. I L

The dyestufis obtained by. the invention are useful not only for dyeing. wool, silk or cotton, but also for dyeing or coloring leather, varnishes and other materials.

The formula of these metal compounds is notknown .The following'examples illustrate theinvention, the parts being by weight Example '1 r 10 parts of the chromium compound of the dyestuff from 'diazetized 1-aminO-Q-hydroxyof the formula naphthalenel-sulfonic acid and u-naphthol are dissolved in 250 parts of boiling water,

partsof the dyestuff from diaz'otized 6-nitro- 2-aminophenol-4=-sulfonic acid and fi-naphthol of the formula NO: OH OH are dissolved inthe solution and the whole is made feebly acid with acetic acid and boiled for a long time in a reflux apparatus. By partial evaporation and salting out the new dyestuif'is obtained. The formula of this chromium compound is not known. It is a blackish powder, soluble in'water and in: caustic soda solution of 10 'per cent. strength to a blackish blue solution and in concentrated sulfuric acid to a greenish blue solution. It dyes wool and silk blackish marine-blue tints of excellent fastness p p erties.

Ewample 2 V A suspension, which has been boiled for a short time, of 45 parts of the dyestuff from V solution.

7 while boiling.

SOaH

nitrated i and 42 parts of the reduction product to a green-blue solution. The formula of this chromium compound is not known. It dyes wool and silk in blue "tints which are exceedingly fast. 7

Example 4 7.88 parts of the azo-dyestuff from l-amino- Q-hydroxynaphthalene-4-sulfonic acid and B- hydroxynaphthalene of the formula HO S N=N- and 4.74 parts of the dyestuff from 2-amino- 1-hydroxynaphthalene-4-sulfonicacid and B- hydroxynaphthalene of the formula of the said dyestuff in 600 parts of water are mixed with 50 parts of crystallized sodium acetate and 55 parts of a solution of chromium formate containing 41. per cent. of Cr O and the mixture is boiled for along time in a reflux apparatus. 360 parts of saturated. common salt solution are then added and boiling continued for 15 hours, after which time chroming is complete. By salting out the boiling solution, there is obtained an. individual chromium compound in the form of a black powder, which dissolves in water to a blue-violet solution, in dilute caustic soda solution to a violet solution and in concentrated sulfuric acidto a blue-black The formula of this chromium compound is not known. The dyestuif dyes wool and silk blue black tints having good properties of fastness.

Example, 3

10 parts of the chormium compound of the azo-dyestuff from l-amino-Q-hydroxynaphthalene-4-sulfonic acid and whydroxynaphthalene are dissolved in 250 parts of water, To this solutionthere are added 2.87 parts of the dyestufi' from diazotized 2-amino-l-hydroxynaphthalene-4: 8- disulfonic acid and fi-hydroxynaphthalene of the formula SOaH HOzS

caustic soda solution of 10 per cent. strength to a violet, and in concentrated sulfuric acid Hogs are dissolved in 300 parts of water, while boiling. To this solution there are then added 12 parts of Cr O in the form of a solution containing 4 per cent. byvolumeof chromium fluoride, andthe reaction mixture is boiled for some time in a reflux apparatus. The dyestuff thus obtained is separated in usual manner. It forms a blackish powder which dissolves in water to a violet, in caustic soda solution of 10. per cent. strength to a red-violet, and in concentrated sulfuric acid to a blackish-blue solution. The formula of this chromium compound is not known. It dyes wool and silk from an acid bath fast blue tintsI' Emample 5 SOaH are together dissolved in 300 parts of water, To this solution there-are iis chromium fluoride, and the reaction mixture is boiled for a long time in areflux apparatus. The new dyestuff is separated in usual V 1 ammo 2 hydroxynaphthalene-l-sulfonic acid and 2phenylammo-5-hydroxy-naphthalene-7-sulfonic acid of the formula on and 8.4 parts of the disazo-dyestufi from 2 mol diazotized 2-amino-1phenol-4-sulfamide and 1 mol 5:5'-dihydroxy-2: 2.-dinaphthylamino-7: 7'-disu1fonic acid of the formula are together dissolved in 500 parts of water. To this there is added a solution of ohro mium fluoride corresponding to l2-parts of c 0 and the whole is heated for some hours while substituting the evaporated Water. The new chromium compound is obtained by concentration and salting out. The 1ormula of this chromium compound is not known. It forms a dark powder which dissolves in water to a blue, in dilute caustic soda solution to a reddish-blue and in concentrated sulfuric acid per cent. of the chromium compound of the azo-dyestufi from diazotized 2-amino-Lhy- S OFNH:

sorNH;

are'together dissolved in 400 parts of water. After addition of a solution of chromium fluoride corresponding to 6rparts of Cir- O the whole is boiled for a long time'in a reflux apparatus. The new metal compound is obtained by evaporation and salting'out- It dissolves in water to a blue,- in dilute caustic soda solution to a reddish-blue, and in concentrated sulfuric acid to a violet solution. The formula of this chromium compound is not known. The dysetuff forms a dark powder and dyes silk and wool from a bath made acid with acetic acid and Viscose and cotton from a neutral bath blue tints.

I Example 7 8.4 parts of the disazo-dyestufi from 2 mol l-phenol and 1 mol 5:'-dihydroxy-2:2- 1v dinaphthylamino-7 :7-disu1fonic acid of the formula 7 H I r V V N=N nozs wuu 'SOaH OH droxy-naphthaleneliS-disulfonic acid and V ,B-naphthol of the formula HQaS on OH SOgH- l per cent. of the chromium compound of the azo-dyestuii from diazotized 1-amino-2- OH uois- Nnwsom et-chlormQ-amino-l-phenol and -1 :8-dihydroxy-naphthalene-3:6-disulfonic acid of the formula r Example 9 A dye-bath is prepared with (calculated on the weight of the goods) 2.4 per cent. of the chromium compound of the azo-dyestuff from diazotized l-amino-2'hydroxynaphthalene-el-sulfonic acid and ,B-naphthol of the formula SOaxH V 0.6 per cent. of the azo-dyestuff from diazotized 5-nitro-2-amino-1-phenol and 2- aminonaphthalene-6-sulfonic acid of the formula ITTH2 OzN SOaH

10 per cent. of Glaubers salt and 2 per cent. of acetic acid. 100 parts of wool are entered at 70 C. and this temperature is maintained for 20 minutes and then raised to boiling; 2 per cent. of concentrated sulfuric acid are added, boiling is continued for half an hour and there are added another 6 per cent. of concentrated sulfuric acid, whereupon dyeing is continued by boiling for 11 hours.

. The goods are then washed and dried. The

wool is dyed marine-blue tints of very good.

properties of fastness.

Instead of chromium other metals which are at least bivalent and which are further capable of yielding complex compounds may be used, such as iron, copper, manganese, nickel, cobalt, vanadium, uranium, titanium, tin or aluminium. Also more than one of these metals may be used together.

What we claim is 5 1. A process for the manufacture of metal compounds of azo-dyestufls, consisting in treating a mixture of different alto-dyestuffs, each containing lake-forming groups, with metal compounds of metals which are at least bivalent, and which are further capable of forming complex compounds.

2. A process for the'manufacture of metal compounds of azo-dyestufis, consisting in treating a mixturerof different o-hydroxyazo-dyestuflfs, with metal compounds of metals which are at leastbivalent, and which are further capable of forming complex compounds.

3. A process for the manufacture of metal compounds of azo-dyestuifs, consisting in treating o-hydroxyazo-dyestufls with metal compounds of o-hydroxy-azo dyestufis of metals which are at least bivalent and which are further capable of forming complex compounds. 7

4. A process for the manufacture of metal compounds of azo-dyestuifs, consisting in treating a mixture of different o-hydroxyazo-dyestufis, with trivalentcompounds of chromium.

5. As new products the new metal .compounds which are obtained by treating a mixture of 'dilferent azo-dyestuffs, each containing lake-forming groups, with metal compounds of metals which are at least bivalent, and which are further capable of forming complex compounds, which products form dark to black powders, dissolving in water to blue-black to blue-violetsolutions and in dilute caustic soda solution to a more or less pure violet solution, dyeing wool-and silk bluish-black tints having good properties of fastness.

6. As new products thernew metal compounds which are obtained by treating a mixture of difierent azo-dyestufl?s, each containing lake-forming groups, with trivalent compounds of chromium, which products form dark to black powders, dissolving in'water to blue-black to blue-violet solutions and in dilute caustic soda solution to a more or less pure violetsolutiomdyeing wool and silk bluish-black tints having good properties of fastness. 1

7. As new products the new metal compounds which are obtained by treating mixtures of different monoazo-dyestufis, each containing lake-forming groups, with metal compounds of metals which are at least bi- -valent, and which are further capable of pounds which are obtained by treating mixtures of monoazo-dyestufi's, each containing lake-forming groups, with trivalent compounds of chromium, which products form dark to black powders, dissolving in water to blue-black to blue-violet solutions and in dilute caustic soda solution to a more or less pure violet solution, dyeing wool and silk bluish-black tints having good properties of fastness.

9. As new products the new metal compounds which are obtained by treating azo dyestuffs with metal compounds of o-hydroxy-azo-dyestufis of metals which are at least bivalent and which are further capable of forming complex compounds, which products form black to dark powders, dissolving in water to blue-black to blue-violet solu-' tions and in dilute caustic soda solution to a more or less violet solution, dyeing wool and silk bluish-black tints having good properties of fastness. p

10. A process of producing complex chromium compounds of o-hydroxy-azo dyestuffs containing less than 1 atom of chromium to each chromable group of the dyestufi' molecule which comprises acting, at an elevated temperature, on a fully chromed o-hydroxy-azo dyestuff with achromiumfree o-hydroxy-azodyestuff,

11. A process of producing complex chromium compounds of o-hydroxy-azo dyestuffs containing less than 1 atom of chromium to each chromable group of the dyestufi' molecule which comprises acting, at an elevated temperature, on a fully chromed ohydroxy-azo dyestufl with a chromium-free o-hydroxy-azo dyestufl Which is different from that of the chromiferous azo dyestufi'.

12. As new articles of manufacture, complex chrominum compoimds which are obtained by heating a fully chromed ohy- V droxy-azo dyestuff with a chromium-free ohydroxy-azo dyestufl which is difierent from that of the chromiferous azo dyestufi.

In witness whereof we have hereunto signed our names this 30th day of August,

FRITZ STRAUB. HERMANN SCHNEIDER. HEINRICH BERNHARD. V 

